Production of acetone from acetylene



' vapor overflcat'alysts comprising naturally Patented Oct. 28, 1930 i "STATES A NT-( m-Ea;

mn'oME MARTIN m) IGNACE VJ. nox- A, or T RM: HAUTE, innI'AnA, ASSIGNORS 'ro V *GOMMEBCIIAL soLvENTs oonro zm'rron, ",DION o mYLnm) .1

or TEBRE HAUTE, INDIANA, A CORPORA- 'rnonuo rloiv or AeEroNE FROM AGETYLENE lo m-awing. Application filed. May. 18,

Our invention, relates to a, process and a catalyst for the production of acetone from acetylene andwater vapor; v 'i We are aware'of the fact that in the-past several investigators have recommended processes for theproduction of acetonefrom acetylene and Water vapor. The 'Elektiizitats- Werke Lonza' (British "Patent, 192,392) de-v scribed a process whereby a'mixtureof 1 part of acetylene" and 2 to 5 parts of steam". was passedat atemp'erature' ranging from 350. toi450 C. over a catalyst comprising a double salt of thorium with an alkali metal or an alkaline earth metal. Austrian Patent No. 88,632, acetone may be obtained by passing a mixture composed of 1 volume of acetylene and 40 volumes of Water occurring forms of iron: such asroasted; pyorites, arglllaceous lron ore, spathlcv iron ore,

let? Austrian Patent O- 8, Specifies that the catalysts be as 'riCh a po in iron oxide,-such as thoseiobtained Joyprecipitating the oxide from ironhydroxide'an'd comf pressing it into ithe fo'rm of tablets Stue'r and Grob '(U, 1?. 1,421,743) state that when acetylene mixed With a small amountof steam is passed at ,a suitable temperature ov'er b'ogr .iron ore, acetone, togethenvvith a'number of other products, is formed; More recently, the Holzverkohlungs-Industrie AktGes. (F1213.

6 l2,11l) has described" the preparation of 1 a cetone by. passing a mixture of' lipartof 1 acetylene tofl-15 volumes of water vaporat .teinperaturesranging from 250" CL to 750 C, cover suitablecatalysts. Catalysts specified, are oxygen;.compo undsof iron','in combinationv with such 'comp'ounds as' manganese oxide, bar um carbonate,- z nc f carbonate,

aluminum ox1de,'1i me and magnesla.

I Oneof are mostefii ient of allot the differ 'ent types of catalysts v'vhichfwe have investi- Unitedstates Patents Nos. 1,625,924,15255- According to gated is that of the character disclosed in 192a Serial No. 334,3;4; .f V a r,

issued 26, 1927, for use-in 'theproduction ofsynthetic methanol. These catalysts com- PIlSG- a plurality of difiic'ultly reducible metal aoxides, a"plurality of easily reducible metal" oxides, anda metallic halide, as, for example, zinc oxide, iron oxide, and zinc chloride;

Below Will be foundfa description of the composition-and method ofpreparing a number of suitable catalysts ofthischaracter; It is distinctly understood, however, that these the character of the catalyst mixtures which We prefer; to useand thatvve arein no way examples are c ted merely as 'llustrativefof bound to theluse of only-the specific examples f cited; Many other combinationsmay' also'be satisfactorily employed in ourpr'ocess.

x1160 nitrate tion, 100 grams zinc oxide are then added I Emm ze lp ,1 f

grams terric ni- 'vvithconstant stirring. "The resulting wet mass isheated in a, porcelainevaporating dish to dryness and'then placed" in a copper. Y

crucible which is heated O'V'GVI' a Fletcher. burner tofdrive' on the fumes of gnit rogen V oxides. The .material thus obtainedgis crushed sufficiently to pass a 65' mesh screen and to; it grams: zinc chloride dissolved inGOcc ater-areadded. The productthus obtained hardens spontaneously.

'8 kilograms oi chlfomicnitrate i I l i 77 v v ,1, 5 kilograms of nickel nitrate are ai'ssav d s izes, of watefl ancl to this solution there is added the theoretical amount (5.4 liters of 12.75 normal) of ammonium hydroxide to precipitate chromium hydroxide and nickel hydroxide. The solution is then centrifuged to recover the precipitated hydroxides and the resultant precipitate is thoroughly washed with water, dried, and broken up into granules. The resultant granules are moistened with an aqueous solution of 200 grams zinc chloride and again dried.

g p g Example V i 8 lgilograms of chromic nitrate ormog en o are dissolved-in 5 liters of water and;

kilograms of zinc oxide added with stirring. The product. thus obtained is evaporated-to dryness and heated until the chromic nitrate is converted to chromic oxide; This material is then mixed With1 10%- of dext'rin or a similar aggll lt-inatingwagent and 640% of zinc chloride,'dissolved in 10 parts of Water. The mixture isthen dried,'brolen up and sieved thru a mesh screen.

Other examplesof' cat'alyst-un'ixtures' of similar character to" the above may be obtainedby suitably combining' material's of thefollowing types;

A One or "morejnon-reducible metal oxides such asz inc', magnesium, cadmium, chromium, vanadium,- tungsten, etc; 1

V One" 'or more easily I redu'c'i'ble metal oxides such as copper, silver, iron, nickel, cobalt-,etc' 1 i (3) A metallic h'alides' Under ordinary circnmstances freshly reduced metals such as iron, cobalt and nickel at elevated temperaturesdecompose acetylene to carbon andhydrogen. The hydrogen resulting from the decomposition of one portion of the gas-may ,then react with a fresh portion to form-ethyleneandethane.- In our improved catalyst combinations, however, this action does not takeplace, or only to a slight extent A .As the result of a series of experiments car.- ried out under similar conditions wlth all .of'the known types of catalysts favoring the ',product ion, of acetone from acetylene and? 'water va'por,'we have found that the cataglysts of: the types which have beendes cri'bed fabovegive more efficacious-resultsthan; any oftheothers: Fore'xample, when passing a mixture composed of 0.12 mols per hour -of acetylene and 1.8'molsper hour of water vapor over 20 cubic centimeters of the catalystdescribed under Example Iabove, at a temperature ranging from 465 485 C., a conversion of 25.0% ofthe acetaylene to acetone was obtained; Under exactly similar,

conditions with the. amount of water vapor increased to 2.0 mols per hour,a conversion of "320% was obtained. i

Q efab ut tQZOiQtthe former. #0:.1: oi

lafter- If athearesidu iznectrlfl after being separated from the acetone, may again be passedover: the catalyst. In such a case, however, it is usually desirable that additional acetylene or water vapon'beaddeli in order to bring the reaction mixture back t'o its optimum;constitution? 1 Now having described our inyent'ion, we claim the following as new'and nove'h A processfor'theproduction of. acetone which comprises "passing a gaseousmixture comprising acetylene] and anexce'ss of water vapor at temperatures ranging from 27 5 C to-725 f" over catalysts initiallycomprising a plurality of diificultly're'ducible metal oxides", a plurality of easilyir'educiblefmetal oxides, and a metallic halide: s, v

. 2; A'pr'ocessfor theproductionof acetone fwh'iehfc'omprises passing a mixturdof one part acetylene and from about 5]60 about 0 parts offwater' vapors temperatures from a oiu e Q i it o 550? C" as cat y initially comprising a -plurality of difii'cultly reducible metal} oxides; 1a pluralityof easily 111 lole" glnet' il foxidesj and :a -metallic halide. 3. A 'proces'sfor theiproduction'of acetone which eomprises agsing a; mixture of one partacetylene and" froinabout ar about-A0 parts of waterivapor at ltem emtures frem about A30 to aboutj5'50 Cfover catalysts initially .comprisinga plurality of diificultly rality ofdiflicufl'tly" reducible metal" oxides from the'thirdjt'o seventh groups'i and metallic halide. '1' f A "process for theproductionso'facetone comprises passing a5 mixture of one part of; acetylene and fromaboutf; tojaliout l-Oiparts of watervapor at temperatures from about 450 to about 550 oyer catalysts "in t a y m p i g z ead i' h u ioxiclelironoxide, and'z'inccliloridei "5. A process 'forfthe production'iof acetone "which 'comprisesf passingfa gaseous mixture 7 comprisingacetylene and anfexcess ofwater vapor at'temperaturesrangfiing from 275 to 725 C. over catalysts initially comprising a plurality of "difficulty reducible met'al' oxides, an easily. reducibl'efrnetal oxide, and a 6. A'process for the production of acetone which comprises passing a gaseous mixture comprising acetyleneand an excess of water,

vapor at temperatures ranging from 275 C.

to 725 C. over catalysts initially comprising a diflicultly reducible metal oxide, an easily reducible metal oxide and a metallic halide.

7 A process for the production of acetone which comprises passing a gaseous mixture comprising acetylene and an excess of Water vapor at temperatures ranging from-275 C. I i to 7 25 C. over catalysts initially comprising. 1 zinc oxide, chromium oxide, iron oxide, and

zinc chloride. I

In testimonywhereof We afl'ix our sigma tures. 1 I JEROMEcMARTIN.

V IGNACE J. KRCHMA. 

